Electrochemically Active LbL Multilayer Films: From Biosensors to Nanocatalysts

Abstract

In this chapter we describe a particular case of layer-by-layer (LbL) multilayer films containing electrochemically or redox active components which can undergo exchange of electrons with an underlying conducting substrate, and ion and solvent exchange with the bathing electrolyte adjacent to the film. In 1997 Laurent and Schlenoff [1] described the electrochemical response of viologen groups in poly(styrenesulfonate)/poly(butanylviologen) LbL thin films and Hodak et al. [2] showed the biosensor response to glucose with the enzyme glucose oxidase (GOx) wired by ferrocene-derivatized poly-(allylamine) LbL multilayers. Since then a large number of publications have described electrochemically active polyelectrolyte multilayers (r-PEMs) including osmium pyridyl-bipyridyl modified poly(allylamines) [3–15], poly(vinylpyridine) osmium complexes [16, 17], ferrocene poly(allylamines [2, 18–20], polyalkylviologens [21–24], sulfonated polyaniline [25], polythiophenes [26], polyoxo-metalates [27–29], enzymes [2, 9–11, 16, 24, 30–33] and redox proteins [34–38], ferrocene-containing poly(amidoamine) dendrimers [39–44], Prussian Blue [45–48], carbon nanotubes [49], metal nanoparticles [50], and so on. The topic has been reviewed elsewhere [51–53]. Electrochemically or redox active polyelectrolyte multilayers (r-PEMs) deposited on conductive substrates (electrodes) and immersed in electrolyte solutions are of particular interest since they have electron acceptors/donors that can exchange electrons with the underlying conductive substrate and propagate redox changes along the direction normal to the substrate. The charge imbalance due to the exchange of electrons between the electrode and the r-PEM results in the transfer of charge across the LbL layers and exchange of solvent and ions with the external electrolyte. In layered thin films the stratified structure results in characteristic behavior and the fuzzy nature of interpenetrated layers facilitates the transfer of charges along the film.films containing electrochemically or redox active components which can undergo exchange of electrons with an underlying conducting substrate, and ion and solvent exchange with the bathing electrolyte adjacent to the film. In 1997 Laurent and Schlenoff [1] described the electrochemical response of viologen groups in poly(styrenesulfonate)/poly(butanylviologen) LbL thin films and Hodak et al. [2] showed the biosensor response to glucose with the enzyme glucose oxidase (GOx) wired by ferrocene-derivatized poly-(allylamine) LbL multilayers. Since then a large number of publications have described electrochemically active polyelectrolyte multilayers (r-PEMs) including osmium pyridyl-bipyridyl modified poly(allylamines) [3–15], poly(vinylpyridine) osmium complexes [16, 17], ferrocene poly(allylamines [2, 18–20], polyalkylviologens [21–24], sulfonated polyaniline [25], polythiophenes [26], polyoxo-metalates [27–29], enzymes [2, 9–11, 16, 24, 30–33] and redox proteins [34–38], ferrocene-containing poly(amidoamine) dendrimers [39–44], Prussian Blue [45–48], carbon nanotubes [49], metal nanoparticles [50], and so on. The topic has been reviewed elsewhere [51–53]. Electrochemically or redox active polyelectrolyte multilayers (r-PEMs) deposited on conductive substrates (electrodes) and immersed in electrolyte solutions are of particular interest since they have electron acceptors/donors that can exchange electrons with the underlying conductive substrate and propagate redox changes along the direction normal to the substrate. The charge imbalance due to the exchange of electrons between the electrode and the r-PEM results in the transfer of charge across the LbL layers and exchange of solvent and ions with the external electrolyte. In layered thin films the stratified structure results in characteristic behavior and the fuzzy nature of interpenetrated layers facilitates the transfer of charges along the film.film. In 1997 Laurent and Schlenoff [1] described the electrochemical response of viologen groups in poly(styrenesulfonate)/poly(butanylviologen) LbL thin films and Hodak et al. [2] showed the biosensor response to glucose with the enzyme glucose oxidase (GOx) wired by ferrocene-derivatized poly-(allylamine) LbL multilayers. Since then a large number of publications have described electrochemically active polyelectrolyte multilayers (r-PEMs) including osmium pyridyl-bipyridyl modified poly(allylamines) [3–15], poly(vinylpyridine) osmium complexes [16, 17], ferrocene poly(allylamines [2, 18–20], polyalkylviologens [21–24], sulfonated polyaniline [25], polythiophenes [26], polyoxo-metalates [27–29], enzymes [2, 9–11, 16, 24, 30–33] and redox proteins [34–38], ferrocene-containing poly(amidoamine) dendrimers [39–44], Prussian Blue [45–48], carbon nanotubes [49], metal nanoparticles [50], and so on. The topic has been reviewed elsewhere [51–53]. Electrochemically or redox active polyelectrolyte multilayers (r-PEMs) deposited on conductive substrates (electrodes) and immersed in electrolyte solutions are of particular interest since they have electron acceptors/donors that can exchange electrons with the underlying conductive substrate and propagate redox changes along the direction normal to the substrate. The charge imbalance due to the exchange of electrons between the electrode and the r-PEM results in the transfer of charge across the LbL layers and exchange of solvent and ions with the external electrolyte. In layered thin films the stratified structure results in characteristic behavior and the fuzzy nature of interpenetrated layers facilitates the transfer of charges along the film.films and Hodak et al. [2] showed the biosensor response to glucose with the enzyme glucose oxidase (GOx) wired by ferrocene-derivatized poly-(allylamine) LbL multilayers. Since then a large number of publications have described electrochemically active polyelectrolyte multilayers (r-PEMs) including osmium pyridyl-bipyridyl modified poly(allylamines) [3–15], poly(vinylpyridine) osmium complexes [16, 17], ferrocene poly(allylamines [2, 18–20], polyalkylviologens [21–24], sulfonated polyaniline [25], polythiophenes [26], polyoxo-metalates [27–29], enzymes [2, 9–11, 16, 24, 30–33] and redox proteins [34–38], ferrocene-containing poly(amidoamine) dendrimers [39–44], Prussian Blue [45–48], carbon nanotubes [49], metal nanoparticles [50], and so on. The topic has been reviewed elsewhere [51–53]. Electrochemically or redox active polyelectrolyte multilayers (r-PEMs) deposited on conductive substrates (electrodes) and immersed in electrolyte solutions are of particular interest since they have electron acceptors/donors that can exchange electrons with the underlying conductive substrate and propagate redox changes along the direction normal to the substrate. The charge imbalance due to the exchange of electrons between the electrode and the r-PEM results in the transfer of charge across the LbL layers and exchange of solvent and ions with the external electrolyte. In layered thin films the stratified structure results in characteristic behavior and the fuzzy nature of interpenetrated layers facilitates the transfer of charges along the film.et al. [2] showed the biosensor response to glucose with the enzyme glucose oxidase (GOx) wired by ferrocene-derivatized poly-(allylamine) LbL multilayers. Since then a large number of publications have described electrochemically active polyelectrolyte multilayers (r-PEMs) including osmium pyridyl-bipyridyl modified poly(allylamines) [3–15], poly(vinylpyridine) osmium complexes [16, 17], ferrocene poly(allylamines [2, 18–20], polyalkylviologens [21–24], sulfonated polyaniline [25], polythiophenes [26], polyoxo-metalates [27–29], enzymes [2, 9–11, 16, 24, 30–33] and redox proteins [34–38], ferrocene-containing poly(amidoamine) dendrimers [39–44], Prussian Blue [45–48], carbon nanotubes [49], metal nanoparticles [50], and so on. The topic has been reviewed elsewhere [51–53]. Electrochemically or redox active polyelectrolyte multilayers (r-PEMs) deposited on conductive substrates (electrodes) and immersed in electrolyte solutions are of particular interest since they have electron acceptors/donors that can exchange electrons with the underlying conductive substrate and propagate redox changes along the direction normal to the substrate. The charge imbalance due to the exchange of electrons between the electrode and the r-PEM results in the transfer of charge across the LbL layers and exchange of solvent and ions with the external electrolyte. In layered thin films the stratified structure results in characteristic behavior and the fuzzy nature of interpenetrated layers facilitates the transfer of charges along the film.fied poly(allylamines) [3–15], poly(vinylpyridine) osmium complexes [16, 17], ferrocene poly(allylamines [2, 18–20], polyalkylviologens [21–24], sulfonated polyaniline [25], polythiophenes [26], polyoxo-metalates [27–29], enzymes [2, 9–11, 16, 24, 30–33] and redox proteins [34–38], ferrocene-containing poly(amidoamine) dendrimers [39–44], Prussian Blue [45–48], carbon nanotubes [49], metal nanoparticles [50], and so on. The topic has been reviewed elsewhere [51–53]. Electrochemically or redox active polyelectrolyte multilayers (r-PEMs) deposited on conductive substrates (electrodes) and immersed in electrolyte solutions are of particular interest since they have electron acceptors/donors that can exchange electrons with the underlying conductive substrate and propagate redox changes along the direction normal to the substrate. The charge imbalance due to the exchange of electrons between the electrode and the r-PEM results in the transfer of charge across the LbL layers and exchange of solvent and ions with the external electrolyte. In layered thin films the stratified structure results in characteristic behavior and the fuzzy nature of interpenetrated layers facilitates the transfer of charges along the film.–20], polyalkylviologens [21–24], sulfonated polyaniline [25], polythiophenes [26], polyoxo-metalates [27–29], enzymes [2, 9–11, 16, 24, 30–33] and redox proteins [34–38], ferrocene-containing poly(amidoamine) dendrimers [39–44], Prussian Blue [45–48], carbon nanotubes [49], metal nanoparticles [50], and so on. The topic has been reviewed elsewhere [51–53]. Electrochemically or redox active polyelectrolyte multilayers (r-PEMs) deposited on conductive substrates (electrodes) and immersed in electrolyte solutions are of particular interest since they have electron acceptors/donors that can exchange electrons with the underlying conductive substrate and propagate redox changes along the direction normal to the substrate. The charge imbalance due to the exchange of electrons between the electrode and the r-PEM results in the transfer of charge across the LbL layers and exchange of solvent and ions with the external electrolyte. In layered thin films the stratified structure results in characteristic behavior and the fuzzy nature of interpenetrated layers facilitates the transfer of charges along the film.–29], enzymes [2, 9–11, 16, 24, 30–33] and redox proteins [34–38], ferrocene-containing poly(amidoamine) dendrimers [39–44], Prussian Blue [45–48], carbon nanotubes [49], metal nanoparticles [50], and so on. The topic has been reviewed elsewhere [51–53]. Electrochemically or redox active polyelectrolyte multilayers (r-PEMs) deposited on conductive substrates (electrodes) and immersed in electrolyte solutions are of particular interest since they have electron acceptors/donors that can exchange electrons with the underlying conductive substrate and propagate redox changes along the direction normal to the substrate. The charge imbalance due to the exchange of electrons between the electrode and the r-PEM results in the transfer of charge across the LbL layers and exchange of solvent and ions with the external electrolyte. In layered thin films the stratified structure results in characteristic behavior and the fuzzy nature of interpenetrated layers facilitates the transfer of charges along the film.–33] and redox proteins [34–38], ferrocene-containing poly(amidoamine) dendrimers [39–44], Prussian Blue [45–48], carbon nanotubes [49], metal nanoparticles [50], and so on. The topic has been reviewed elsewhere [51–53]. Electrochemically or redox active polyelectrolyte multilayers (r-PEMs) deposited on conductive substrates (electrodes) and immersed in electrolyte solutions are of particular interest since they have electron acceptors/donors that can exchange electrons with the underlying conductive substrate and propagate redox changes along the direction normal to the substrate. The charge imbalance due to the exchange of electrons between the electrode and the r-PEM results in the transfer of charge across the LbL layers and exchange of solvent and ions with the external electrolyte. In layered thin films the stratified structure results in characteristic behavior and the fuzzy nature of interpenetrated layers facilitates the transfer of charges along the film.–44], Prussian Blue [45–48], carbon nanotubes [49], metal nanoparticles [50], and so on. The topic has been reviewed elsewhere [51–53]. Electrochemically or redox active polyelectrolyte multilayers (r-PEMs) deposited on conductive substrates (electrodes) and immersed in electrolyte solutions are of particular interest since they have electron acceptors/donors that can exchange electrons with the underlying conductive substrate and propagate redox changes along the direction normal to the substrate. The charge imbalance due to the exchange of electrons between the electrode and the r-PEM results in the transfer of charge across the LbL layers and exchange of solvent and ions with the external electrolyte. In layered thin films the stratified structure results in characteristic behavior and the fuzzy nature of interpenetrated layers facilitates the transfer of charges along the film.–53]. Electrochemically or redox active polyelectrolyte multilayers (r-PEMs) deposited on conductive substrates (electrodes) and immersed in electrolyte solutions are of particular interest since they have electron acceptors/donors that can exchange electrons with the underlying conductive substrate and propagate redox changes along the direction normal to the substrate. The charge imbalance due to the exchange of electrons between the electrode and the r-PEM results in the transfer of charge across the LbL layers and exchange of solvent and ions with the external electrolyte. In layered thin films the stratified structure results in characteristic behavior and the fuzzy nature of interpenetrated layers facilitates the transfer of charges along the film.films the stratified structure results in characteristic behavior and the fuzzy nature of interpenetrated layers facilitates the transfer of charges along the film.